The development of efficient, high-performance materials for electrical energy storage and conversion applications has become a must to meet an ever-increasing need for electrical energy. Among devices developed for this purpose, capacitors have been used for pulsed power applications that require large power density with millisecond-scale charge and discharge. However, conventional polymeric films, which possess high breakdown strength, are limited due to low permittivity and hence compromise the energy storage capability of capacitors. In order to develop high energy density dielectric materials for pulsed power applications, two hurdles must be overcome: 1) the appropriate selection of materials that possess not only large permittivity but also high breakdown strength, 2) the optimization of material processing to improve morphology of dielectric films to minimize loss during energy extraction process. This thesis will present the development of novel dielectric material, with emphasis on the optimization of material and thin film processing toward improved morphology as ways to achieve high energy density at the material level. After first two chapters of introduction and experimental details, Chapter 3 will demonstrate the improvement of nanocomposite morphology via processing optimization and study its effect on the energy storage characteristics of nanocomposites thereof. Chapter 4 will investigate dielectric sol-gel materials containing dipolar cyano side groups, which are relatively a new class of material for pulsed power applications. Finally, Chapter 5 will discuss the effect of tunneling barrier layer on sol-gel films to mitigate charge carrier injection and associated conduction and breakdown phenomena, which would be significantly detrimental to the energy storage performance of dielectric sol-gel films.

Nanocomposites with expandable smectites such as montmorillonite layered silicates (MLS) in polymer matrices have attracted extensive application interest. Numerous MLS concentrations have been used with no particular justification. Here, we investigate the effects of MLS dispersion within the matrix and on mechanical performance. The latter is resolved through a three-prong investigation on rate dependent tensile results, time dependent creep results and the influence of a sharp notch in polypropylene (PP) nanocomposites. A fixed concentration of maleated polypropylene (mPP) was utilized as a compatibilizer between the MLS and non-polar PP. Analysis of transmission electron micrographs and X-ray diffraction patterns on the surface and below the surface of our samples revealed a unique skin-core effect induced by the presence of clay. Differential scanning calorimetric and polarized optical microscopic examination of spherulites sizes showed changes in nucleation and growth resulting from both the maleated PP compatibilizer and the MLS. These structural changes resulted in a tough nanocomposite, a concept not reported before in the PP literature. Nonlinear creep analysis of the materials showed two concentrations 3 and 5 % wt of PP, which reduced the compliance in the base PP. The use of thermal wave imaging allowed the identification of ductile failure among materials, but more important, aided the mapping of the elastic and plastic contributions. These are essential concepts in fracture analysis.

Research on metal nanoparticles (MNPs) synthesis and their applications for optoelectronic devices has been a recent interest in the fields of nanoscience and nanotechnology Photovoltaics are one of such systems in which MNPs have shown to be quite useful, due to unique physical, optical, magnetic, and electronic properties, including the metal nanoparticles synthesized in this research. Owing to the challenges with the most common physical and chemical methods of preparing MNPs, including the use of high temperatures, toxic reducing agents, and environmentally hazardous organic solvents, there is a critical need for a benign synthesis procedure for MNPs. In this work, a simple, versatile, and environmentally and economically responsible synthesis method for making iron, nickel, zinc, and bimetallic alloy nanoparticles (ANPs) has been developed and functionalization with organic capping agents were performed to form metal-organic hybrid nanocomposites with tunable properties. The size, shape, elemental composition, photophysical properties, and crystallinity of particles and their hybrids have been evaluated. Monometallic nanostructures of iron, nickel, and zinc oxide were synthesized via aqueous-phase reduction of metal(II) chloride salts with sodium borohydride. Upon optimization of the standard method described here, reaction parameters like reaction time, reagent molar ratios, and capping-agent molar ratio were evaluated. Characterization techniques such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive x-ray (EDS), IR, and UV-visible spectroscopies, selected area electron diffraction (SAED), and power x-ray diffraction (XRD) were performed as necessary. Well-defined, reproducible nickel and iron nanoparticles were produced with average diameters of 26±4 nm and 50±26 nm, respectively, arranged into chain-like structures. Much smaller (6-9 nm) zinc oxide particles that self-assembled into single-particle thick, hexagonal hierarchical microstructures were formed from a modified standard method. Similarly, iron-nickel ANPs with the average size of 20.9±3.3 nm were also synthesized and successful grafting with the polymer capping agent, polyvinylpyrrolidone was confirmed. Because of size, ordered self-assembly, and benign synthesis procedure, the nanoparticles described here are ideal candidates for photovoltaic and thermoelectric device applications. Moreover, these particles have shown to disperse well in various organic and inorganic media, and therefore have wide versatility in thin-film deposition methods.

Master of Science / Department of Mechanical and Nuclear Engineering / Gurpreet Singh / 3D-printing is a popular manufacturing technique for making complex parts or small quantity batches. Currently, the applications of 3D-printing are limited by the material properties of the printed material. The processing parameters of commonly available 3D printing processes constrain the materials used to a small set of primarily plastic materials, which have relatively low strength and electrical conductivity. Adding filler materials has the potential to improve these properties and expand the applications of 3D printed material. Carbon nanomaterials show promise as filler materials due to their extremely high conductivity, strength, and surface area. In this work, Graphite, Carbon Nanotubes, and Carbon Black (CB) were mixed with raw Acrylonitrile Butadiene Styrene (ABS) pellets. The resulting mixture was extruded to form a composite filament. Tensile test specimens and electrical conductivity specimens were manufactured by Fused Deposition Method (FDM) 3D-printing using this composite filament as the feedstock material. Weight percentages of filler materials were varied from 0-20 wt% to see the effect of increasing filler loading on the composite materials. Additional tensile test specimens were fabricated and post-processed with heat and microwave irradiation in attempt to improve adhesion between layers of the 3D-printed materials. Electrical Impedance Spectroscopy tests on 15 wt% Multiwalled Carbon Nanotube (MWCNT) composite specimens showed an increase in DC electrical conductivity of over 6 orders of magnitude compared to neat ABS samples. This 15 wt% specimen had DC electrical conductivity of 8.74x10−6 S/cm, indicating semi-conducting behavior. MWCNT specimens with under 5 wt% filler loading and Graphite specimens with under 1 wt% filler loading showed strong insulating behavior similar to neat ABS. Tensile tests showed increases in tensile strength at 5 wt% CB and 0.5 wt% MWCNT. Placing the specimens in the oven at 135 °C for an hour caused increased the stiffness of the composite specimens.

Research into the processing conditions and parameters of polymeric nanocomposites has always been challenging to scientists and engineers alike. Many have developed tools and procedures to allow materials to be exploited and their properties improved with the addition of nanofillers to achieve the desired end material for various applications. Initial trials are mostly conducted using conventional small scale experiments using specialised equipment within the laboratory that can replicate the larger industrial equipment. This is a logical approach as it could save time and costs as many nanocomposites are relatively expensive to produce. Experiments have previously been done using the likes of the Haake twin screw extruder to manufacture nanocomposites within the laboratory but this research project has used a novel minimixer specifically developed to replicate mixing like large twin screw extrusion machines. The minimixer uses a twin paddle system for high shear mixing in conjunction with a single screw thus theoretically allowing an infinitely long recirculation. It is this ability to mix intensely whilst allowing for as long as desired recirculation which enables the replication in this very small mixer (10-30g capacity) of the mixing conditions in a large twin screw extruder. An added feature of the minimixer is that it can undertake inline data analysis in real time. The main experiments were conducted using a comprehensive DOE approach with several different factors being used including the temperature, screw speed, residence time, clay and compatibiliser loading and two polymer MFI's. The materials used included PP, Cloisite 20A, Polybond 3200, PET, Somasif MTE, Polyurethane 80A and Single / Multi-walled Carbon nanotubes. Detailed experimental results highlighted that rheological analysis of the nanocomposite materials as an initial testing tool were accurate in determining the Elastic and Loss modulus values together with the Creep and Recovery, Viscosity and Phase Angle properties in the molten state. This approach was also used in an additional set of experiments whereby the temperature, speed, residence time and compatibiliser were kept constant but the clay loading was increased in 1% wt. increments. These results showed that the G' & G'' values increased with clay loading. Another important finding was the bi-axial stretching step introduced after the processing stage of the nanocomposite materials which highlighted a further improvement in the modulus values using rheological testing. Other tests included using inline monitoring to look into both the viscosity and ultrasound measurements in real time of the molten polymer nanocomposite through a slit die attachment to the minimixer.

The processing and properties of novel polymer-based nano-composite (PNC) dielectrics for capacitor applications has been studied. PNCs were fabricated via a vacuum based deposition technique and their micro/nano-structure, chemical and dielectric properties investigated. After process development and optimisation, co-deposited Al and nylon-6 PNCs had a dielectric constant k∼7 at an approximate Al volume fraction of 0.3 that agreed with analytical predictions if it was assumed that the Al transformed to an oxide in-situ and/or after deposition. The significant effect of absorbed water vapour and temperature on PNC dielectric properties was revealed using different types of post-deposition heat treatment. Alternately-deposited PNCs consisting of Al or Ag 2-20 nm layers sandwiched between nylon-6 layers were fabricated in which the overall PNC Al or Ag volume fraction was controlled by varying the nominal Al or Ag layer thickness. Ag layers comprised of discrete nano-islands that produced a nano-capacitor network effect that increased k to ∼11. In the case of Al layers, when the layer thickness was ≥ 5 nm, corresponding to a nominal volume fraction of 0.1, Al (core)-oxide (shell) nanoparticles were formed and the PNC dielectric constant increased to ∼19. The detailed nano-structure of the core-shell particles was studied using various types of transmission electron microscopy (TEM), and the elevations in dielectric constant ascribed to multiple-interface polarisation effects dependent on the formation of the core-shell structure. PNCs based on alternate deposition of Ti sandwiched in nylon-6, and then both Ti and Ag in nylon-6 were also fabricated, with k reaching ∼73 for Ag+Ti/nylon-6 PNCs. As well as Ti-based core (metal)-shell (oxide) particles, the Ag volume fraction was sufficiently high in the 10 nm nylon-6 layers to again form a nano-capacitor network that contributed to the overall device capacitance and effective dielectric constant. Again, various types of high magnification TEM were critical in resolving the Ti-based core-shell structure and its role in high-k behaviour. The vacuum-based alternate deposition technique has been developed to offer ease of operation, reliability, flexibility and applicability to chemically different filler and matrix systems in the fabrication of high-k PNC based capacitors, in which high-k performance relies critically on the formation of core (metal)-shell (oxide) particles in both Al and Ti based systems.

L'objectif de ce travail est l'élaboration de nouveaux matériaux nanocomposites hybrides à propriétés spécifiques (piézoélectricité, optique non-linéaire). Dans un premier temps, des modèles numériques simples portant sur les propriétés mécaniques des nanocomposites sont présentées, ainsi que des simulations de déformation réalisées sur les nanocomposites à nanoparticules piézoélectriques. Les résultats expérimentaux de caractérisation mécanique (par spectrométrie Brillouin) et tribologique de différents nanocomposites sont exposés, y compris de nanocomposites réalisés au sein du laboratoire. L'influence des nanoparticules et de leur fonctionnalisation sur la matrice polymère y est discutée, et en particulier leur incidence sur les volumes libres dans les nanocomposites. Plusieurs procédés de synthèse de nanoparticules aux propriétés piézoélectriques ont parallèlement été étudiées. En particulier, un protocole de synthèse de nanoparticules de LiNbO3 a été mis au point. Ces nanoparticules ont été caractérisées par des techniques structurales, chimiques et d'imagerie. Enfin, ces travaux ont conduit à l'élaboration de films nanocomposites à matrice PVDF-TrFE incorporant des nanoparticules produites en laboratoire ou d'origine commerciale. Les méthodes de polarisation des films sont décrites, et les propriétés piézoélectriques de ces films nanocomposites ont été mesurées. Plus particulièrement, des films nanocomposites PVDF-TrFE/Al2O3 polarisés présentant une bonne réponse piézoélectrique ont été élaborés. / This work aims at the elaboration of new hybrid nanocomposites with specific properties (piezoelectricity, non-linear optic). First, simple numeric modelings on mechanical properties of nanocomposites are presented, as well as simulation of deformation in nanocomposites with piezoelectric nanoparticles. Experimental results on tribological and mechanical (performed by Brillouin Spectroscopy) characterization of different nanocomposites are exposed. The influence of nanoparticles and their fonctionalization on the polymer matrix is discussed, and in particular the incidence on free volume in nanocomposites. Several piezoelectric nanoparticles synthesis processes have been also studied. In particular, a LiNbO3 nanoparticles synthesis protocol has been worked out. These nanoparticles were characterized by structural, chemical and imaging techniques. Finally, these works leads to the elaboration of PVDF-TrFE matrix thin films nanocomposites filled with commercial or produced in laboratory nanoparticles. The methods used to polarize the films are described. The piezoelectric properties of the nanocomposites have been measured. More particularly, PVDF-TrFE/Al2O3 nanocomposites thin films with a good piezoelectric response have been elaborated.

L’incorporation de nanotubes de carbone dans une matrice polymère permet d’obtenir des matériaux nanocomposites avec des propriétés exceptionnelles. Toutefois, ces dernières dépendent de l’état de dispersion et distribution des nanotubes dans la matrice. Afin de conférer de meilleures propriétés, il est essentiel que le procédé de synthèse des nanocomposites permette une répartition contrôlée des nanotubes dans la matrice. Un procédé de polymérisation in situ, en présence de nanotubes de carbone, a été choisi. Ce dernier permet de contrôler la répartition des nanotubes dans la matrice grâce à l’utilisation des ultrasons. Afin d’optimiser ce procédé, et notamment lors de la polymérisation anionique activée de l’e-caprolactame, l’influence de la présence des nanotubes sur la vitesse de polymérisation et les propriétés rhéologiques du milieu polymérisant a été déterminée. Grâce à une étude calorimétrique suivie d’une étude rhéocinétique, il a été démontré que la présence de nanotubes ralentit la polymérisation et augmente fortement la viscosité du milieu. Cette inhibition provient probablement d’une réaction entre les nanotubes et le catalyseur utilisé pour la polymérisation et dépend donc de l’état de dispersion des nanotubes dans la matrice, lequel peut ainsi être estimé par les études cinétiques. L’étude des propriétés rhéologiques et électriques des nanocomposites à matrice polystyrène et à renforts de nanotubes de carbone a également été entreprise. Suivant l’état de dispersion ainsi que les différents paramètres opératoires, les seuils de percolation électrique et rhéologique ont ainsi pu être déterminés / The introduction of carbon nanotubes into polymers leads to nanocomposite materials with exceptional properties. These later depend, however, on the dispersion and distribution of carbon nanotubes inside the matrix. A key objective, in nanocomposite preparation, is the set up of incorporation processes allowing a good state of dispersion of the nanotubes into the matrix. An in situ polymerization process, coupled with an ultrasound processor, was chosen to best fulfill this objective. The optimization of this process implies the knowledge of the evolution of reaction kinetics and rheological properties during the polymerization. The influence of carbon nanotubes on the anionic activated polymerization of e-caprolactam was investigated by calorimetric and rheokinetic studies. Carbon nanotubes were found to slow down polymerization kinetics and highly increase the viscosity after a certain conversion degree. This inhibition phenomenon could be produced by a reaction between carbon nanotubes and the catalyst employed for the polymerization reaction. The inhibition effect depended also on the state of dispersion of the nanotubes, consequently, kinetic and rheokinetic measurements are an indirect method to estimate the state of dispersion. The electrical and rheological properties of the nanocomposites were also investigated. The influence of the state of dispersion and other parameters, such as temperature, on the electrical and rheological percolation thresholds was identified

The ability to encapsulate/insert different kinds of nanoparticles (NPs) in scrolled nanosheets (NSs) may lead to the formation of new nanocomposite materials that yield novel properties. These nanostructures resemble “peapods” that consist of NPs chains (“peas”) located in a hollow space of desired nanoscrolls (“pods”). Depending on different combinations of “peas” and “pods” diverse families of nanopeapods (NPPs) can be synthesized which may exhibit interesting properties not accessible from the individual components. Though there exist various synthetic methods for the formation of NPPs, more development in terms of simplicity, flexibility, and productivity of synthetic approaches are needed so that different classes of NPPs with unique combinations/characteristics of “peas” and “pods” can be synthesized. A simple solvothermal synthesis method for the encapsulation of spherical Fe3O4 NPs by the capture of preformed NPs in scrolled hexaniobate has previously been developed in our group. In the first part of this research, efforts were made to extend the “pod” materials to other inorganic NScs. Vanadate nanoscrolls (NScs) could rapidly (2h) be produced using a simple solvothermal treatment in the presence of V2O5 as vanadium source, and either dodecylamine (DDA) or octadecylamine (ODA) as the structure-directing agent. The synthesis parameters were successfully adjusted to obtain high yields vanadate NScs (~ 20 g of NScs per synthesis) with different average lengths as 383 nm, 816 nm to 3.3 µm. The effects of reaction time on the formation of NScs were also investigated. Further efforts focused on the development of methods for making vanadate NPPs. Here, two novel approaches for the formation of these NPPs have been successfully developed. In the first, solvothermal methods utilizing preformed Ag NPs and vanadate NSs lead to the formation of Ag@vanadate NPPs where NPs could be encapsulated during the scrolling of NSs. High NP loadings were acquired with this approach. In the second method, an insertion strategy was developed where Ag NPs were drawn into the lumen of preformed vanadate NScs upon controlled solvent evaporation. This method was also quite effective, though much lower loadings of NPs were achieved with larger average NP-NP distances. Also noteworthy in the study of vanadate NScs and NPPs is the observation of an uncommon asymmetric scrolling behavior; this was realized for both vanadate NScs and solvothermally synthesized Ag@vanadate NPPs. Novel solvothermal approaches for the effective construction of organic-MoOx hybrid structures and MoOx nanosheets (NSs) have also been developed. These NSs can be controlled so as to exist in different oxidation states as well as in different crystal structures. Layer spacing as a function of organic molecule lengths could also be controlled by changing the type of surfactants located between the NSs. Individual NSs or a few layers of stacked NSs, up to four micrometers in lateral size were successfully prepared upon sonication. The effect of time, temperature, as well as the type of structure-directing agents on the formation and crystal structure of MoOx intercalated compound/NSs were also explored. Lastly, a modified solvothermal method previously used for the encapsulation of spherical Fe3O4 NPs inside hexaniobate NScs was applied for the construction of cubic-CeO2 NPPs. High yield encapsulations of preformed cubic ~5 nm ceria NPs within the lumen of hexaniobate NScs were readily accomplished. Size selective encapsulation and the formation mechanism of cubic-CeO2 NPPs were also studied. Pre-organization and attachment of ceria NPs to the surface/edges of hexaniobate crystals prior to the scrolling process were observed, which is in a good agreement with our previous studies on the formation mechanism of NPPs. Partially filled CeO2@hexaniobate NPPs were further used in the in-situ growth of gold NPs within the empty/hollow space of hexaniobate NScs. This led to the formation of high-quality Au-CeO2@hexaniobate NPPs. We believe that smart combinations of the methods for the formation of NPPs, encapsulation, in-situ growth and insertion, will allow one to acquire other classes of nanocomposite materials composed of different types, shapes, and arrangements of NPs in the hollow spaces of distinct NTs/NScs.

Ph.D. (Chemistry) / This study addressed the incorporation of nanotechnology-based materials, either through incorporating nanomaterials or by introducing nanostructures onto the membrane matrix, to form nano-enabled polymeric membranes with high specific flux and better anti-fouling profile. The aim of the study was to integrate nanotechnology and membrane science in order to improve the performance of water filtration membranes by alleviating some of the specific shortcomings of water treatment membranes......